CN110922865A - Steel surface composite coating and preparation method thereof - Google Patents
Steel surface composite coating and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
Abstract
The invention discloses a steel surface composite coating, which relates to the technical field of steel corrosion prevention and comprises the following raw materials in parts by weight: 20-30 parts of 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, 13-17 parts of graphene oxide, 400 parts of waterborne acrylic modified epoxy resin, 20-30 parts of methyl tetrahydrophthalic anhydride, 20-30 parts of methyl nadic anhydride and 10-20 parts of pyromellitic anhydride. The composite coating has excellent corrosion resistance, can effectively prevent seawater from corroding steel materials, has excellent friction resistance and blue algae resistance, and is suitable for coating the surfaces of pipelines and ships in the sea.
Description
Technical Field
The invention relates to the technical field of steel corrosion prevention, in particular to a steel surface composite coating and a preparation method thereof.
Background
Steel is the most widely used metal material in the manufacturing industry, and can be processed into various friction parts as an important metal material in the industry. When the steel material is used as a friction part, the phenomena of surface corrosion, abrasion and the like are easy to occur in the operation process, and the service life of the steel part is shortened. Especially with the development of marine engineering in China, various cross-sea bridges, port construction, marine oil and gas field development, marine equipment, ship engineering, submarine pipelines and the like are pulled out like bamboo shoots in the spring after rain, and steel structure materials play an increasingly important role in marine economy. However, due to the corrosion of seawater and the adhesion and mass propagation of seaweeds, various steel structure materials inevitably suffer from serious corrosion problems in the long-term service process, and the phenomenon not only restricts the service life of the steel structure, but also brings great potential safety hazards.
The epoxy resin has the characteristics of excellent mechanical property, good cohesiveness, stable mechanical strength and the like, and meanwhile, the epoxy resin has strong oil resistance and alkali resistance, and is an organic coating which has the most requirements and the most extensive application in the field of corrosion prevention of marine equipment and facilities at present. Therefore, coating the epoxy resin on the surface of the steel is a main mode for solving the problem at present, but the epoxy resin coating has the problems of weak bonding force with the steel matrix, poor wear resistance and the like in practical application. These problems can lead to corrosion and damage of the coating under some extreme conditions, reducing the tribological and corrosion resistance properties of the epoxy coating.
Disclosure of Invention
In order to solve the problems, the invention provides a steel surface composite coating and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: the composite coating on the surface of the steel comprises the following raw materials in parts by weight: 20-30 parts of 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, 13-17 parts of graphene oxide, 400 parts of waterborne acrylic modified epoxy resin, 20-30 parts of methyl tetrahydrophthalic anhydride, 20-30 parts of methyl nadic anhydride and 10-20 parts of pyromellitic anhydride.
Further, the composite coating comprises the following raw materials in parts by weight: 20 parts of 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, 13 parts of graphene oxide, 300 parts of waterborne acrylic modified epoxy resin, 20 parts of methyl tetrahydrophthalic anhydride, 20 parts of methyl nadic anhydride and 10 parts of pyromellitic anhydride.
Further, the feed comprises the following raw materials in parts by weight: 30 parts of 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, 17 parts of graphene oxide, 400 parts of waterborne acrylic modified epoxy resin, 30 parts of methyl tetrahydrophthalic anhydride, 30 parts of methyl nadic anhydride and 20 parts of pyromellitic anhydride.
Further, the feed comprises the following raw materials in parts by weight: 25 parts of 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, 15 parts of graphene oxide, 350 parts of waterborne acrylic modified epoxy resin, 25 parts of methyl tetrahydrophthalic anhydride, 25 parts of methyl nadic anhydride and 15 parts of pyromellitic anhydride. The invention also provides a preparation method of the steel surface composite coating, which comprises the following steps:
s1, weighing the 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, dissolving in a proper amount of isopropanol, and stirring until the mixture is completely dissolved;
s2, weighing the graphene oxide, dissolving the graphene oxide in a proper amount of deionized water, heating in a water bath at 40 ℃, and magnetically stirring until the graphene oxide is completely dissolved;
s3, slowly dripping the graphene aqueous solution in the step S2 into the 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine isopropanol solution in the S1 while stirring, and keeping a water bath at 45 ℃ in the stirring process; stirring for 2 hours after the dropwise addition is finished;
s4, sealing and placing the mixed solution obtained in the step S3 for 48 hours, performing ultrasonic treatment for 30min to obtain modified graphene oxide, and then volatilizing to remove redundant isopropanol;
s5, adding the modified graphene oxide obtained in the step S4 into the waterborne acrylic acid modified epoxy resin, and stirring the mixture until the mixture is uniformly mixed;
s6, uniformly mixing the methyltetrahydrophthalic anhydride, the methylnadic anhydride and the pyromellitic anhydride according to the parts by weight, adding the mixture into the epoxy resin S5, magnetically stirring for 2 hours, and removing bubbles by ultrasonic treatment for 20 minutes to obtain the epoxy resin composite coating.
Further, in the step S3, the slow dropping speed is 10 to 20 drops/min.
Further, the ultrasonic power in step S4 is 1600W-1800W.
The invention has the beneficial effects that:
the 4-2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine modifies the graphene oxide, and the pi bonds on the naphthalenesulfonic acid and the pi electrons of the adjacent graphene oxide are interacted, so that the dispersibility of the graphene oxide is improved, and the performance of the graphene oxide is better;
in the process of preparing the composite coating, the dropping speed of the graphene aqueous solution into the 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine isopropanol solution is controlled to be 10-20 drops/minute, so that the bonding rate of the graphene and the 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine can be improved, the agglomeration phenomenon is avoided, and the prepared coating has better bonding performance with steel.
The composite coating has excellent corrosion resistance, wear resistance and hydrophobicity, can resist the adhesion of algae, and is suitable for coating the surface of marine steel.
The proportion between the epoxy resin and the curing agent can directly influence the perfection degree of a three-dimensional network structure of a cured product, and further influence the mechanical and electrical properties and other properties of the cured product.
In addition to the objects, features and advantages described above, other objects, features and advantages of the present invention are also provided. The present invention will be described in further detail below with reference to the drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a graph of corrosion rate of a steel surface composite coating in NaCl solution according to the invention;
FIG. 2 is a friction coefficient diagram of a steel surface composite coating according to the present invention;
FIG. 3 shows a composite coating OD on the surface of steel680A graph of values;
FIG. 4 is a graph of the adhesion rate of the composite coating on the surface of steel according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1 to 2, as shown in fig. 1 to 2, an embodiment of a steel surface composite coating and a method for preparing the same according to the present invention is as follows:
example 1
The composite coating on the surface of the steel comprises the following raw materials: 2g of 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, 1.3g of graphene oxide, 30g of aqueous acrylic acid modified epoxy resin, 2g of methyl tetrahydrophthalic anhydride, 2g of methyl nadic anhydride and 1g of pyromellitic anhydride.
The preparation method of the steel surface composite coating comprises the following steps:
s1, weighing 2g of 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, dissolving in a proper amount of isopropanol, and stirring until the solution is completely dissolved;
s2, weighing 1.3g of graphene oxide, dissolving the graphene oxide in a proper amount of deionized water, heating the graphene oxide in a water bath at 40 ℃, and magnetically stirring the graphene oxide until the graphene oxide is completely dissolved;
s3, slowly dripping the graphene aqueous solution in the step S2 into the 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine isopropanol solution in the S1 while stirring, wherein the dripping speed is 10 drops/min, and keeping a water bath at 45 ℃ in the stirring process; stirring for 2 hours after the dropwise addition is finished;
s4, sealing and placing the mixed solution obtained in the step S3 for 48 hours, performing ultrasonic treatment for 30 minutes at the ultrasonic power of 1600W to obtain modified graphene oxide, and then volatilizing to remove redundant isopropanol;
s5, adding the modified graphene oxide obtained in the step S4 into 30g of waterborne acrylic acid modified epoxy resin, and stirring while adding until the materials are uniformly mixed;
s6, then uniformly mixing 2g of methyl tetrahydrophthalic anhydride, 2g of methyl nadic anhydride and 1g of pyromellitic anhydride, adding the mixture into the epoxy resin S5, magnetically stirring for 2h, and removing bubbles by ultrasonic treatment for 20min to obtain the epoxy resin composite coating.
Example 2
The composite coating on the surface of the steel comprises the following raw materials: 3g of 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, 1.7g of graphene oxide, 40g of waterborne acrylic modified epoxy resin, 3g of methyl tetrahydrophthalic anhydride, 3g of methyl nadic anhydride and 2g of pyromellitic anhydride.
The preparation method of the steel surface composite coating comprises the following steps:
s1, weighing 3g of 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, dissolving in a proper amount of isopropanol, and stirring until the solution is completely dissolved;
s2, weighing 1.7g of graphene oxide, dissolving the graphene oxide in a proper amount of deionized water, heating the graphene oxide in a water bath at 40 ℃, and magnetically stirring the graphene oxide until the graphene oxide is completely dissolved;
s3, slowly dripping the graphene aqueous solution in the step S2 into the 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine isopropanol solution in the S1 while stirring, wherein the dripping speed is 13 drops/min, and keeping a water bath at 45 ℃ in the stirring process; stirring for 2 hours after the dropwise addition is finished;
s4, sealing and placing the mixed solution obtained in the step S3 for 48 hours, then carrying out ultrasonic treatment for 30 minutes at the ultrasonic power of 1800W to obtain modified graphene oxide, and then volatilizing to remove redundant isopropanol;
s5, adding the modified graphene oxide obtained in the step S4 into 40g of waterborne acrylic acid modified epoxy resin, and stirring while adding until the mixture is uniformly mixed;
s6, then 3g of methyl tetrahydrophthalic anhydride, 3g of methyl nadic anhydride and 2g of pyromellitic anhydride are uniformly mixed and added into the epoxy resin S5, the mixture is magnetically stirred for 2 hours, and air bubbles are removed by ultrasonic treatment for 20min to obtain the epoxy resin composite coating.
Example 3
The composite coating on the surface of the steel comprises the following raw materials: 2.5g of 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, 1.5g of graphene oxide, 35g of aqueous acrylic modified epoxy resin, 2.5g of methyl tetrahydrophthalic anhydride, 2.5g of methyl nadic anhydride and 1.5g of pyromellitic anhydride.
The preparation method of the steel surface composite coating comprises the following steps:
s1, weighing 2.5g of 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, dissolving in a proper amount of isopropanol, and stirring until the solution is completely dissolved;
s2, weighing 1.5g of graphene oxide, dissolving the graphene oxide in a proper amount of deionized water, heating the graphene oxide in a water bath at 40 ℃, and magnetically stirring the graphene oxide until the graphene oxide is completely dissolved;
s3, slowly dripping the graphene aqueous solution in the step S2 into the 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine isopropanol solution in the S1 while stirring, wherein the dripping speed is 17 drops/minute, and keeping a water bath at 45 ℃ in the stirring process; stirring for 2 hours after the dropwise addition is finished;
s4, sealing and placing the mixed solution obtained in the step S3 for 48 hours, performing ultrasonic treatment for 30 minutes at the ultrasonic power of 1600W to obtain modified graphene oxide, and then volatilizing to remove redundant isopropanol;
s5, adding the modified graphene oxide obtained in the step S4 into 35g of waterborne acrylic acid modified epoxy resin, and stirring while adding until the mixture is uniformly mixed;
s6, then uniformly mixing 2.5g of methyl tetrahydrophthalic anhydride, 2.5g of methyl nadic anhydride and 1.5g of pyromellitic anhydride, adding the mixture into the epoxy resin of S5, magnetically stirring for 2 hours, and removing bubbles by ultrasonic treatment for 20min to obtain the epoxy resin composite coating.
Example 4
The composite coating on the surface of the steel comprises the following raw materials: 2g of 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, 1.7g of graphene oxide, 30g of aqueous acrylic acid modified epoxy resin, 2g of methyl tetrahydrophthalic anhydride, 2g of methyl nadic anhydride and 2g of pyromellitic anhydride.
The preparation method of the steel surface composite coating comprises the following steps:
s1, weighing 2g of 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, dissolving in a proper amount of isopropanol, and stirring until the solution is completely dissolved;
s2, weighing 1.7g of graphene oxide, dissolving the graphene oxide in a proper amount of deionized water, heating the graphene oxide in a water bath at 40 ℃, and magnetically stirring the graphene oxide until the graphene oxide is completely dissolved;
s3, slowly dripping the graphene aqueous solution in the step S2 into the 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine isopropanol solution in the S1 while stirring, wherein the dripping speed is 20 drops/minute, and the water bath is kept at 45 ℃ in the stirring process; stirring for 2 hours after the dropwise addition is finished;
s4, sealing and placing the mixed solution obtained in the step S3 for 48 hours, then carrying out ultrasonic treatment for 30 minutes at the ultrasonic power of 1800W to obtain modified graphene oxide, and then volatilizing to remove redundant isopropanol;
s5, adding the modified graphene oxide obtained in the step S4 into 30g of waterborne acrylic acid modified epoxy resin, and stirring while adding until the mixture is uniformly mixed;
s6, then uniformly mixing 2g of methyl tetrahydrophthalic anhydride, 2g of methyl nadic anhydride and 2g of pyromellitic anhydride, adding the mixture into the epoxy resin S5, magnetically stirring for 2 hours, and removing bubbles by ultrasonic treatment for 20 minutes to obtain the epoxy resin composite coating.
Comparative example 1
Graphene oxide was not modified with 2-tert-butylamino-4-ethylamino-6-methylsulfanyl-1, 3, 5-triazine, and the other preparation steps were the same as in example 1.
Experimental example 1
The application of the steel surface composite coating on the steel surface specifically comprises the following steps:
s8, cleaning oil stains and an oxidation layer on the surface of the AH32 ship plate steel which is made of the same materials and has the thickness of 20cm by 20cm, cleaning the oil stains and the oxidation layer on the surface of the ship plate steel by using a detergent, an acid solution and an alkali solution, and airing the ship plate steel after the cleaning is finished;
s9, uniformly coating the composite coatings of the embodiments 1-4 and the comparative example 1 on the surface of the steel plate, laying and placing for 20min after coating, and then placing in a drying oven at 90 ℃ for drying.
Experimental example 2: performance testing of composite coatings
In order to test the hydrophobic property of the composite coating of the present invention, a contact angle tester was used to measure the static Contact Angle (CA) of the coating, the contact angles of the composite coatings of examples 1-4 were 89 °, 92 °, 91 °, and 91 °, respectively, and the contact angle of the composite coating of comparative example 1 was 83 °, indicating that the hydrophobic property of the composite coating of the present invention is better.
To determine the corrosion resistance of the composite coatings prepared in example 2 of the present invention and comparative example 1, 6 steel plates having the same size were coated with the composite coatings of example 2 and comparative example 1 by the method of example 1, and the corrosion resistance of the coating was tested without coating any other steel plate. And respectively putting the prepared steel plates into 3.5wt% NaCl solution at room temperature, taking out the samples every 10 days, washing out corrosion products on the surfaces, and calculating the corrosion rate V (F) of the samples according to the weight loss rate of the samples in unit area and unit time. The smaller the value of V (F), the better the seawater corrosion resistance of the sample. The value calculation formula of V (F) is shown in formula (1).
W in formula (1)0And W1The mass g of the steel plate sample before and after corrosion respectively; a is the area of the sample in m2(ii) a t is the time for soaking the sample in saline water, d; v (F) is the corrosion rate, g/(m)2*d）。
In the test, it is found that when the coated sample is soaked for 16 days, a small amount of corrosion spots appear when the uncoated sample is soaked for 15 days, the surface of the coated steel plate has no change, a large amount of corrosion spots appear on the uncoated steel plate in 32 days, a large amount of brown corrosion substances appear in the solution, 3 corrosion spots with the sizes of needle points appear on the steel plate coated with the coating of the comparative example 1, the surfaces of the steel plates coated with the examples 1 to 4 have no change, about 60 percent of the uncoated steel plate is covered with the corrosion substances and the oxides in 60 days, the corrosion spots with the sizes of mung bean particles appear on the composite coated steel plate coated with the comparative example 1, a small amount of corrosion substances exist in water, and the surface of the steel plate coated with the composite coating of the example 2 is obviously changed.
The results of the corrosion rate calculation are shown in FIG. 1, and it can be seen from FIG. 1 that the uncoated steel sheet was used for 10 daysThe water is corroded by sodium chloride solution at the corrosion rate of 0.08, the corrosion rate is continuously increased along with the increase of the soaking time, and the corrosion rate reaches 0.2 g/(m) at 60 days2D), the steel sheet coated with the composite coating of comparative example 1 was corroded by the sodium chloride solution only 20 days later and the corrosion rate was much lower than that of the steel sheet without the coating, the steel sheet coated with the composite coating of example 2 was not corroded by the sodium chloride solution within 60 days, and the negative corrosion rate was caused by the fact that the steel sheet absorbed moisture after being placed in the sodium chloride solution, increasing the weight of the steel sheet, and allowing W to pass through the steel sheet1＞W0So a negative value occurs.
Experimental example 3: experiment of coefficient of friction
The friction and wear test is carried out by using an SFT-2M type ball disc type friction and wear tester, the main function of the device is to detect the dynamic friction coefficient in real time when the friction and wear test is carried out on a sample, and the tribological performance of the sample is evaluated by testing the friction coefficient and the wear amount of the sample. First using the material
A steel ball of 60Cr having a diameter of 5mm was subjected to a ball-and-disk type point contact friction test on the steel sheet samples prepared in experimental example 1 to test the tribological properties of the composite coatings of examples 1 to 4 of the present invention and comparative example 1. The rotating speed of the objective table is set to be 100r/min, the radius of the abrasion circle is 3mm, the applied load of the weight load platform is 200g, and the test time is 10 min. The results are shown in fig. 2, and it can be seen from the figure that after the graphene oxide modified by 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine is added into the composite coating, the wear resistance of the composite coating can be effectively improved by curing the composite coating with a mixture of methyl tetrahydrophthalic anhydride, methyl nadic anhydride and pyromellitic anhydride, so that the friction coefficient is reduced from 0.89 to about 0.35.
Experimental example 4: algae resistance experiment
The coating surface is polluted by chlorella serving as model algae, in order to observe the adhesion/growth condition of the chlorella on the coating surface, a coating sample coated on the steel surface is used for carrying out an anti-pollution experiment, and the coating anti-algae adhesion/growth performance is evaluated by a turbidity method and a laser copolymerization set microscope (CLSM)Can be used. To quantify the amount of chlorella adhered/grown on the surface of the coating layer, the chlorella on the surface of the steel sheet coated with the composite coating layers of examples 1-4 and comparative example 1 was detached and resuspended in 1ml of a pbs solution, and the OD of the chlorella solution was tested680The results are shown in figure 2, and it can be seen from the figure that the composite coating prepared by the invention can effectively inhibit the adhesion of algae on the surface of steel, and the OD of the algae liquid can be adjusted by adding 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine680The value decreases from 0.024 to around 0.1.
In order to further quantify the adhesion condition of chlorella on the surfaces of different epoxy resin coatings, the area of the small chlorella adhered to the surface of the steel coating is measured, and the adhesion rate of the small chlorella is obtained by dividing the adhesion area of the small chlorella by the surface area of steel, and the result is shown in figure 3, wherein the adhesion rate of the small chlorella in the composite coatings prepared in the examples 1-4 of the invention is reduced from 9.6% to about 2% compared with the composite coating of the comparative example.
2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine modifies graphene oxide, and due to the interaction between a large pi bond on a naphthalene sulfonic acid benzene ring and pi electrons of adjacent graphene oxide, the dispersibility of the graphene oxide is improved, and the performance of the graphene oxide is better;
in the process of preparing the composite coating, the dropping speed of the graphene aqueous solution into the 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine isopropanol solution is controlled to be 10-20 drops/minute, so that the bonding rate of the graphene and the 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine can be improved, the agglomeration phenomenon is avoided, and the prepared coating has better bonding performance with steel.
The composite coating has excellent corrosion resistance, wear resistance and hydrophobicity, can resist the adhesion of algae, and is suitable for coating the surface of marine steel;
the proportion between the epoxy resin and the curing agent can directly influence the perfection degree of a three-dimensional network structure of a cured product, and further influence the mechanical and electrical properties and other properties of the cured product.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. The steel surface composite coating is characterized by comprising the following raw materials in parts by weight: 20-30 parts of 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, 13-17 parts of graphene oxide, 400 parts of waterborne acrylic modified epoxy resin, 20-30 parts of methyl tetrahydrophthalic anhydride, 20-30 parts of methyl nadic anhydride and 10-20 parts of pyromellitic anhydride.
2. The steel surface composite coating according to claim 1, comprising the following raw materials in parts by weight: 20 parts of 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, 13 parts of graphene oxide, 300 parts of waterborne acrylic modified epoxy resin, 20 parts of methyl tetrahydrophthalic anhydride, 20 parts of methyl nadic anhydride and 10 parts of pyromellitic anhydride.
3. The steel surface composite coating according to claim 1, comprising the following raw materials in parts by weight: 30 parts of 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, 17 parts of graphene oxide, 400 parts of waterborne acrylic modified epoxy resin, 30 parts of methyl tetrahydrophthalic anhydride, 30 parts of methyl nadic anhydride and 20 parts of pyromellitic anhydride.
4. The steel surface composite coating according to claim 1, comprising the following raw materials in parts by weight: 25 parts of 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, 15 parts of graphene oxide, 350 parts of waterborne acrylic modified epoxy resin, 25 parts of methyl tetrahydrophthalic anhydride, 25 parts of methyl nadic anhydride and 15 parts of pyromellitic anhydride.
5. The method for preparing a composite coating on a steel surface according to any one of claims 1 to 4, comprising the following steps:
s1, weighing the 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine, dissolving in a proper amount of isopropanol, and stirring until the mixture is completely dissolved;
s2, weighing the graphene oxide, dissolving the graphene oxide in a proper amount of deionized water, heating in a water bath at 40 ℃, and magnetically stirring until the graphene oxide is completely dissolved;
s3, slowly dripping the graphene aqueous solution in the step S2 into the 2-tert-butylamino-4-ethylamino-6-methylthio-1, 3, 5-triazine isopropanol solution in the S1 while stirring, and keeping a water bath at 45 ℃ in the stirring process; stirring for 2 hours after the dropwise addition is finished;
s4, sealing and placing the mixed solution obtained in the step S3 for 48 hours, performing ultrasonic treatment for 30min to obtain modified graphene oxide, and then volatilizing to remove redundant isopropanol;
s5, adding the modified graphene oxide obtained in the step S4 into the waterborne acrylic acid modified epoxy resin, and stirring the mixture until the mixture is uniformly mixed;
s6, uniformly mixing the methyltetrahydrophthalic anhydride, the methylnadic anhydride and the pyromellitic anhydride according to the parts by weight, adding the mixture into the epoxy resin S5, magnetically stirring for 2 hours, and removing bubbles by ultrasonic treatment for 20 minutes to obtain the epoxy resin composite coating.
6. The method for preparing the composite coating on the surface of the steel as claimed in claim 5, wherein the slow dropping speed in the step S3 is 10-20 drops/min.
7. The method for preparing the composite coating on the surface of the steel as claimed in claim 5, wherein the ultrasonic power in the step S4 is 1600W-1800W.
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